Method of preparing phenolic compounds



Patented Feb. I, 1938 METHOD OF PREPARING PHENOLIC COM- POUNDS John F. Olin, Grosse lle, Mlch., asslgnor to The Sharples Solvents Corporation, Philadelphia, Pa.

No Drawing. Application December 6, 1935, Serial No. 53,210

19 Claims.

The present invention pertains to the condensation of unsaturated hydrocarbons and their derivatives with aromatic compounds, such as phenols, cresols, naphthols, etc., having an by substantially to exclude reaction of the less reactive ingredient of the mixture with the aromatic compound.

In the practice of the Grosscup invention, a

droxyl radical substituted for a nuclear hydrogen mixture of oleflns was first treated with the atom. An example of such a condensation reacphenolic compound to be condensed at substantlon is the condensation of trimethyl ethylene tially normal temperature. A very small trace with phenol to produce para tertiary amyl of an acid adapted to act as a catalyst was therephenol. I after added to the mixture of phenol and hydrom The invention was conceived in connection with carbon and intimately mixed therewith, the mixresearch upon the problem of condensing olefin ture being refluxed to cause a preliminary reachydrocarbons with phenol to produce para alkyl tion to take place between the olefin and the phenols and it is particularly useful in connec- P e c c p un t treatment being Care- F tion with an operation of that character. In an fully controlled to prevent the reaction of the r operation of this kind,'it is usually important that phenolic co ou d with the olefin material in the desired para alkyl compound be produced in the mixture other than that which it was desired a form in which it contains only a very small to condense. proportion of impurities in the nature of di-alkyl The mixture of reacted and unreacted matephenols, sulphonic acids, ethers, ortho-alkyl rial was next distilled and the heads p s of! phenols and other products of incidental reacat a temperature within the boiling range of the tions which may occur in connection with the olefin were separately collected. The residue was production of the ortho-alkyl compound. thereafter digested by heating it to a temperature In the prior patent of William M. Lee and Lee adapted to cause a conversion of the reaction H. Clark, No. 2,050,188, dated August 4, 1936 and products of the olefin and phe s a ment the application of Charles G. Grosscup, Serial No. being continued for a considerable period of time 25 662.528, filed March 24, 1933 processes were dein rd r t efl t su s n ly pl t onscribed in which para alkyl phenols are produced version or the initial condensation product. from crude materials comprising as principal re- While the operation above described resulted actants phenol on the one hand and an isomeric in import t economies Over the D 0 ee and mixture of olei'ins on the other. These applica- Clark process described in Patent 2,050,188, it tions describe and claim processes whose object yielded a p uc Whose melting ran e indicated is to effect the reaction of a mixture of olefin that it did not possess the optimum desirable dematerial containing two or more oleilns of which area of purity. While the applicant does not M at least one is more reactive than the other or wish to be limited to any particular chemical others with phenol in such a manner as to effect theory with respect to the present invention, it selective reaction 01 the more reactive ingredient is his opinion that the degree of impurity present 01' the mixture to the substantial exclusion of the in the Grosscup product was largely attributable remainder. to the following causes:

An illustrative example of a process which may 1. The removal of the less reactive olefin, such 40 be carried out by operations such as disclosed in as the pentene 2 from a mixture of pentene 2 and the Lee and Clark and Grosscupapplications is trimethyl ethylene, by distillation, resulted in unthe condensation with phenol of trimethyl ethyldesired condensation with the phenol present of ene from a mixture of isomeric oleflns including a part of the material whose removal waslsought 4 pentene 2 to the virtual exclusion of the pentene 2 and consequent contamination of the desired which is present in the isomeric mixture. While phenolic derivative with this material.

the processes disclosed in these co-pending appli- The Pract O the fin l d e t n operation cations have been relatively successful in the in the presence of sulphuric acid and of acetic practice of such operations, the relative proporacid resulted in the production of a number of tion of impurities present in the desired paraundesired by-products, suchas acetates, etc. The 50 tertiary amyl phenol is larger than desired and occurrence of these undesired reactions also reit is the particular object of the present invention suited in a reduction of the yield which might to eflect a selective condensation as described in be obtained from the practice of such a process these applications, and particularly in the Gross-v under more nearly ideal conditions, and a further cupappllcatlon, in such a manner as to mateobject of the present invention has been to imrially reduce the quantity of such impurities. It prove the yields obtained by the Grosscup and Lee is thereiore another object of the present invenand Clark processes. tion to condense a mixture of more reactive and The present invention rests upon the discovless reactive oleiins with an hydroxy aromatic ery that a. modification of the Grosscup process compound, such as phenol, in such a manner as by which the acid used in connection with the on -maybeusedwith initial condensation step'is neutraliled, the in-' termediate product thereafter subjected to a distillation operation, andfinally digested with aluminum chloride, zinc chloride. ferric chlorider sulphuric acid or other equivalent rearranging catalyst. results in a very substantial improve- 1m, although. llnc chloride has also been found to be useful and other talysts known to the art tlal improvement over the Grosscup results. provided the acid used in the initial condensation reaction be neutralised before distillation of the initial reaction .mixture to eifect removal of unreacted olefin and dehydration. It will thus be seen that the fundamentahfeature of the invention consists in the nullification of thecatalytic eifect of the acid condensing agent of the Cirosscup process upon the less reactive olefin and phenol which occurred in the distillation step of the Grosscup process, by neutralization of this acid catalyst prior to such distillation and that the present invention contemplates fundamentally the performance of this neutralization step and the subsequent rearrangement operation in the presence of other catalysts than that which was used in the initial condensation.

The detailed procedure of the present invention in the treatment of a mixture of olefins containing a more reactive and a less reactive ingredient to condense the more reactive ingredient with phenol to the substantial exclusion of the less reactive ingredient and to produce a para alkyl derivative by condensation of the more reactive ingredient with phenol is as follows: The mixture of oleflns. such for example as a mixture of trimethyl ethylene and pentene 2, is first intimately mixed with a quantity of phenol constituting a molecular equivalent of the olefin to be reacted, or somewhat more than the molecular equivalent, and a small quantity of an acid catalyst is thereafter added to the mixture so produced. Reaction between the more reactive ingredient and the phenol commences immediately and is controlled by refiux and external cooling. when the reaction has proceeded to the desired extent, the catalytic acid is neutral ized and unreacted olefin is thereafter distilled from the mixture. At the completion of the distillation of the unreacted olefin. the condensation product which consists of a variety of compounds is further distilled to remove water and other undesired compounds. The remaining mixture isthen cooled and the rearrangement catalyst is added. The rearrangement is accomplished by heating the mixture to which the rearrangement catalyst has been added for a sufilcient length of time to accomplish the maximum degree of conversion of undesired side reaction products into the desired phenolic derivative. The following detailed examples illustrate the practice of the process.

amylene mixture containing approximately 50% normal amylenes and 50% branched chain amylenes were placed in a 12 liter fiask and same during the addition of 20 cc. of concentrated. sulphuric acid thereto. Immediate reac- -tion set in and this reaction was moderated by reflux and external cooling to maintain the reaction temperature at about 45 C. The material was allowed to stand over night and 57 grams of 50% sodium hydroxide solution were added while stirring the mixture. Unreacted amylene was distilled ofi between 30 and 40 C.

and was found to weigh 155'! grams.

The amylene. so recovered was of remarkable purity. having an Engler distillation range between 34? and 36.6 C, This boiling range indicates only one isomer, (pentene2), a'fact further substantiated by routine analysis of the ma- ]terial which showed 0% isoamylene.

" After the pentene 2'was distilled off, the fractionation was continued until a temperature of 180 C. was reached, thus efiecting removal of the water andsmall amounts of hexane and hexylene which were present as impurities in the initial olefin mixture and of diamvlene incldentally formed in the practice of the preceding parts of the process. The contents of the flask were cooled to C. and 50 grams of anhydrous aluminum chloride powder were added. Rearrangement was then accomplished by heating for one hour on an oil bath at a temperature between and C. After cooling the mixture so produced to 100 C., the crude tertiary amyl phenol was washed with 1000 cc. of 1% hydrochloric acid solution and 1000 cc. of hot water, (to remove aluminum chloride) and finally with 1000 cc. of 1% sodium carbonate solution. Upon distillation at atmospheric pressure through a x 5 cm. packed column, the following cuts were obtained:

Cut No. Weight Identity 60 Water am lens Phenol y Ortho tertiary amyl phenol Para tertiary amyl phenol I man. n m ism spointsi) V c ersio -s|.s villi 280.0%

Example 2 Condensation of amylene and phenol was effected as in the prior example. The crudecondensatlon product was neutralized and dehydrated by distillation. The mass was thereafter Cut No. 3:21 Weight Identity Gram i. To 150' Water. amyelna. 1%,.- 13 Srtho isrtiary ylpbanol am 4 sac-am i740 Pars-mien au iglrphenol M 11 ll Residue- $2 Conversion-58% Yield-04% Emple 3 20 mols of phenol and'3000 grams of mixed amylene were condensed,'neutralised and dehydratedasinthepriorexamples. 25cc.ofcon- I acid thereto.

centrated' sulphuric acid were then added to the refluxed mixture and the heating continued at 140 C. for four hours more, at the end 01' which time rearrangement appearedcomplete. The material was thereafter washed and fractionated and yielded the following-cuts:

Cut Nos 36;}:{ Weight Identity Grams 170200 24B Phenol axe-250 68 Ortho and para tertiary nmyl phenol 250457 2100 Pam tertiary amyl phenol (softening point 80.5") Reslduo- 394 Conversion 05.9 Yieid= 6% Example 4 2950 grams of ortho cresol and 4096 grams of an amyiene mixture similar to that of Example 1 were placed in a 12 liter flask and stirred during the addition of 25 cc. of concentrated sulphuric Immediate reaction set in and this reaction was moderated by external cooling to maintain the reaction temperature at about 45 C.

" The material was neutralized and distilled to remove water and olefin as in Example 1. The

contents of the flask were then cooled to 80 C.

and 50 grams of aluminum chloride were added. Rearrangement was then accomplished by heating for two hours at a temperature of 140 C. and the resulting material was washed, neutralized and distilled to yield the following cuts:

Boiling v point Identity Cut No. Weight Grams 121 Ortlio crcsol 72 Intermediate 1027 Tertiary amyl ortho cresol The tertiary 'amyl ortho cresoi is a pale yellow viscous o v Eaample 5 2320 grams of mixed liquid normal and isobutylenescontain'ing 2320 grams of iso-butylene and 2209 grams-of phenol'were placed in a bronze autoclavetogether with 20 cc. of concentrated sulphuric acid. The materials were stirred for minutes and thereafter allowed to stand for 24 hours. On opening the autoclave aportion of the normaL-butylene evaporated. The remaining material was placed in-a 12 liter flask, neutralized f byladditionof 285 grams 10 NaOH, the remain- 'in'g normal butylene evaporated off and the maj terial dried by distillation. The crude ortho ter- ,tiary butyl phenol was then isomerized by heating 2 hours with 60 grams AlzCls at 140 0., and, after washing in the usual manner, distilled.

While I have described the above invention specifically with respect to an operation in;which a mixture of oleflns is condensed with phenol in such a manner as to efiect selective condensation therefore wish to be limited except ited to this detailed procedure, as the feature 01 condensation in the presence oi! an acid catalyst and subsequent rearrangement in the presence of one of the catalysts described above, and preferably in the presence of aluminum chloride, will probably find utility in connection with thepractice of condensation operations in which but a single olefln or other unsaturated hydrocarbon is to be condensed with an aromatic hydroxy compound in which an hydroxyl radical is substituted in the nucleus. Other modifications will be obviousto those skilled in the art and I do not by the scope of the sub-joined claims.

I claim:

1. The method of effecting reaction between an unsaturated hydrocarbon and an aromatic compound substituted in the nucleus by an hydroxyl radical which comprises effecting initial condensation between the aromatic compound and said .unsaturated hydrocarbon in the presence of an acid catalyst, neutralizing the acid catalyst, and thereafter effecting rearrangement of the reaction products so produced by heating in the presence of a Friedel and Crafts catalyst.

2. The method of effecting reaction between an unsaturated hydrocarbon and an aromatic compound substituted in the nuclem of an hydroxyl radical which comprises effecting initial condensation between the aromatic compound and said unsaturated hydrocarbon in the presence of an acid catalyst, neutralizing the acid catalyst, and thereafter efiecting rearrangement of y the reaction products so produced by heating in the presence of a catalyst chosen from the class catalyst, and thereafter effecting rearrangement of the reaction products so produced by heating 4. The method of eifecting selective reaction bon mixture and an aromatic compound substituted imthe nucleus by an hydroxyl radical which comprises effecting initial condensation between the aromatic compound and the more reactive port-ion of said'unsaturated hydrocarbon mixture in the presence of an acid catalyst under condidltions controlled to substantially preclude reaction between said aromatic compound and the less reactive portion of said unsaturated hydrocarbon mixture, neutralizing the acid catalyst, and thereafter efiecting rearrangement of the reaction products so produced by heating in the presence of a Friedel and Crafts catalyst.

5. The method of effecting selective reaction between-a portion of an olefin mixtureand an aromatic compound substituted in the nucleus by an hydroxyl radical which comprises effecting initial condensation between the aromatic compound and the more reactive portion of said olefin mixture in the presence of an acid catalyst under conditions controlled to substantially preclude reaction between said aromatic compound and the less reactive portion of said olefin mixture, neutralizing the acid catalyst, and thereafter effecting rearrangement of the reaction products in the presence of a Friedel and Crafts catalyst.

so produced by heating in the presence of a Friedel and Crafts catalyst.

6. The method of eii'ectingv selective reaction between a portion of an unsaturated hydrocarbon mixture and an aromatic compound substituted in the nucleus by an hydroxyl radical which comprises effecting initial condensation between the aromatic compound and the more reactive portion of said unsaturated hydrocarbon mixture in the presence of an acid catalyst under conditions controlled to substantially preclude reaction between said aromatic compound and the less reactive portion of said unsaturated hydrocarbon mixture, neutralizing the acid catalyst, distilling the less reactive olefin material from the condensation product and thereafter efi'ecting rearrangement of the reaction products so produced by heating in the presence of a Friedel and Crafts catalyst.

'7. The method of efiecting selective reaction between a portion of an unsaturated hydrocarbon mixture and an aromaticcompound substituted in the nucleus by an hydroxyl radical which comprises eifecting initial condensation between the aromatic compound and the more reactive portion of said unsaturated hydrocarbon mixture in the presence of an acid catalyst under conditions controlled to substantially preclude reaction between said aromatic compound and the less reactive portion of said unsaturated hydrocarbon mixture, neutralizing the acid catalyst, distilling the less reactive olefin material from the condensation product and thereafter efiecting rearrangement of the reaction products so produced by heating in the presence'of a catalyst chosen from the class consisting of sulphuric acid, aluminum chloride, zinc chloride and ferric chloride.

8. The method'of eflecting selective reaction between ingredients of an isomeric olefin mixture comprising branch chain and normal olefin and an aromatic compound substituted in the nucleus by an hydroxyl radical which comprises eil'ecting initial condensation between the aromatic compound and the branch chain olefin oi the mixture in the presence of an acid catalyst under conditions controlled to substantially preclude reaction between said aromatic compound and the normal olefin of the mixture, neutralizing the acid catalyst, removing the normal olefin from the reaction mixture and thereafter effecting rearrangement of the reaction products so produced by heating in the presence of a Friedel and Crafts catalyst.

9. The method of eflecting selective reaction between ingredients of an isomeric olefin'mixture comprising branch chain and normal olefin and an aromatic compound substituted in the nucleus by an hydroxyl radical which comprises effecting initial condensation between the aromatic compound and the branch chain olefin of the mixture in the presence of an acid catalyst under conditions controlled to substantially preclude reaction between said aromatic compound and the normal olefin of the mixture, neutralizing the acid catalyst, removing the normal olefin from the reaction mixture and thereafter eii'ecting rearrangement of the reaction products so produced by heating in the presence of a catalyst chosen from the. class consisting of aluminum chloride, zinc chloride, ferric chloride and sulphuric acid.

10. The method of efiecting selective reaction between ingredients of an isomeric olefin mixture comprising branch chain and normal olefin and an aromatic compound substituted in the nucleus by an hydroxyl radical which comprises effectinginitial condensation between the aromatic compound and the branch chain olefin of the mix-. ture in the presence of an acid catalyst under conditions controlled to substantially preclude reaction between said aromatic compound and the normal olefin oi the mixture, neutralizing the acid catalyst, removing the normal olefin from the reaction mixture and thereafter eil'ecting rearrangement of the reaction products so produced by heating in the presence of aluminum chloride.

11. The method of producing para tertiary amyl phenol which comprises mixing an olefin composition containing branch chain amylene and normal amylene with phenol and eifecting initial condensation between the phenol and the branch chain amylene in the presence of an acid catalyst under conditions controlled to substantially preclude reaction between the phenol and normal amylene, neutralizing the acid catalyst, removing normal amylene from the mixture by distillation and thereafter effecting rearrangement of the reaction products so produced by heating in the presence of a Friedel and .Crafts catalyst.

12. The method of producing para tertiary amyl phenol which comprises mixing an olefin composition containing branch chain amylene and normal amylene with phenol and effecting initial condensation between the phenol and the branch chain amylene in the presence of an acid catalyst under conditions controlled to substantially preclude reaction between the phenol and normal amylene, neutralizing the acid catalyst, removing normal amylene from the mixture by distillation I and thereafter effecting rearrangement of the reactionproducts so produced by heating in the presence of aluminum chloride.

13. Themethod of effecting selective reaction between an amylene mixture containing branch chain amylene and normal amylene and an aromatic compound substituted in the nucleus by an hydroxyl radical which comprises effecting initial condensation between the aromatic compound and the branch chain amylene of the mixture in the presence of 'an acid catalyst under conditions controlled to substantially preclude reaction between the normal amylene of the mixture and said aromatic compound, neutralizing the acid catalyst, removing the normal amylene by distillation and thereafter effecting rearrangement of the reaction products so produced by heating in the presence of a Friedel and Crafts catalyst.

14. The method of efiecting selective reaction between an amylene mixture containing branch chain amylene and normal amylene and an arcmatic compound substituted in the nucleus by an hydroxyl radical which comprises effecting initial condensation between the aromatic compound and the branch chain amylene of the mixture in the presence of an acid catalyst under conditions controlled to substantially preclude reaction between the normal amylene oi the mixture and said aromatic compound, neutralizing the acid catalyst, removing the normal amylene by distillation and thereafter eflecting rearrangement of the reaction products so produced by heating in the presence oi a catalyst chosen from the class consisting of aluminum chloride, zinc chloride, ferric chloride and sulphuric acid.

15. The method of eflecting selective reaction between an amylene mixture containing branch chain amylene and normal amylene and an aromatic compound substituted in the nucleus by an hydroxyl radical which comprises effecting initial condensation between the aromatic compound and the branch chain amylene oi the mixture in the presence of an acid catalyst under conditions controlled tosubstantially preclude reaction between the normal amylene of the mixture and said aromatic compound, neutralizthe normal amylene, neutralizing the acid catalyst, removing normal amylene from the mix- Patent No. 2,107,060.

ture by distillation and thereafter eii'ecting rearrangement oi the reaction products so produced by heating in the presence of a Friedel and Crafts catalyst.

the presence of a Frledel and Crafts catalyst.

JOHN F. OLIN.

CERTIFICATE OFJCORRECTI ON. I

February 1, 1958.

JOHN F. OLIN.

ing the acid catalyst, removing the normal am- 18. The method of producing para-tertiary 5 ylene by distillation and thereafter effecting rebutyl phenol which comprises mixing an olefin arrangement of the reaction products so procomposition containing branch chain butyiene duced by heating in the presence of aluminum and normal butylene with phenol and effecting chloride. initial condensation between the phenol and the 16. The method of producing a para-tertiary branch chain butylene in the presence of an acid 1 alkyl cresol which comprises mixing an olefin catalyst under conditions controlled to substancomposition containing branch chain olefin and tially preclude reaction between the phenol and normal olefin with cresol and effecting initial normal butylene, neutralizing the acid catalyst, condensation between the cresol and the branch removing normal butylene from the mixture by. chain olefin in the presence of an acid catalyst distillation and thereafter effecting rearrange- 15 under conditions controlled to substantially prement of the reaction products so produced ,by elude reaction between the cresol and the normal heating in the presence of a Friedel and Crafts olefin, neutralizing the acid catalyst, removing catalyst. normal olefin from the mixture by distillation 19. The method of producing a para-tertiary and thereafter effecting rearrangement of the alkyl phenol which comprises mixing an olefin 20 reaction products so produced by heating in the composition containing branch chain olefin and presence of a Friedel and Crafts catalyst. normal olefin with phenol and effecting initial 17. The method of producing a para-tertiary condensation between the phenol and the branch amyl cresol which comprises mixing an olefin chain olefin in the presence of an acid catalyst composition containing branch chain amylene under conditions controlled to substantially pre- 25 and normal amylene with cresol and effecting clude reaction between the phenol and the norinitial condensation between the cresol and the ma] olefin, neutralizing the acid catalyst, rebranch chain amylene in the presence of an acid moving normal olefin from the mixture by distilcatalyst under conditions controlled to substanlation and thereafter effecting rearrangement of tially preclude reaction between the cresol and the reaction products so produced by heating in 30 of the above numbered patent requiring correction as follows: Page 3-,seco'ml' (Seal) It is hereby certified that error appears in the printed specification column, line 50, claim 2', for theword "of" read by; andgthat the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office. I

Signed and sealed this li th day of June, A. 1). 19

Henry Van Arsdale, Acting Commissioner of Patents.

ture in the presence of an acid catalyst under conditions controlled tosubstantially preclude reaction between the normal amylene of the mixture and said aromatic compound, neutralizthe normal amylene, neutralizing the acid catalyst, removing normal amylene from the mix- Patent No. 2,107,060.

ture by distillation and thereafter eii'ecting rearrangement oi the reaction products so produced by heating in the presence of a Friedel and Crafts catalyst.

the presence of a Frledel and Crafts catalyst.

JOHN F. OLIN.

CERTIFICATE OFJCORRECTI ON. I

February 1, 1958.

JOHN F. OLIN.

ing the acid catalyst, removing the normal am- 18. The method of producing para-tertiary 5 ylene by distillation and thereafter effecting rebutyl phenol which comprises mixing an olefin arrangement of the reaction products so procomposition containing branch chain butyiene duced by heating in the presence of aluminum and normal butylene with phenol and effecting chloride. initial condensation between the phenol and the 16. The method of producing a para-tertiary branch chain butylene in the presence of an acid 1 alkyl cresol which comprises mixing an olefin catalyst under conditions controlled to substancomposition containing branch chain olefin and tially preclude reaction between the phenol and normal olefin with cresol and effecting initial normal butylene, neutralizing the acid catalyst, condensation between the cresol and the branch removing normal butylene from the mixture by. chain olefin in the presence of an acid catalyst distillation and thereafter effecting rearrange- 15 under conditions controlled to substantially prement of the reaction products so produced ,by elude reaction between the cresol and the normal heating in the presence of a Friedel and Crafts olefin, neutralizing the acid catalyst, removing catalyst. normal olefin from the mixture by distillation 19. The method of producing a para-tertiary and thereafter effecting rearrangement of the alkyl phenol which comprises mixing an olefin 20 reaction products so produced by heating in the composition containing branch chain olefin and presence of a Friedel and Crafts catalyst. normal olefin with phenol and effecting initial 17. The method of producing a para-tertiary condensation between the phenol and the branch amyl cresol which comprises mixing an olefin chain olefin in the presence of an acid catalyst composition containing branch chain amylene under conditions controlled to substantially pre- 25 and normal amylene with cresol and effecting clude reaction between the phenol and the norinitial condensation between the cresol and the ma] olefin, neutralizing the acid catalyst, rebranch chain amylene in the presence of an acid moving normal olefin from the mixture by distilcatalyst under conditions controlled to substanlation and thereafter effecting rearrangement of tially preclude reaction between the cresol and the reaction products so produced by heating in 30 of the above numbered patent requiring correction as follows: Page 3-,seco'ml' (Seal) It is hereby certified that error appears in the printed specification column, line 50, claim 2', for theword "of" read by; andgthat the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office. I

Signed and sealed this li th day of June, A. 1). 19

Henry Van Arsdale, Acting Commissioner of Patents. 

